Process for breaking petroleum emulsions



55 tented duty 25, 193% tars arise PROCESS FOR BREAKING PETRQLEUll l EMULSKONS Melvin Dc Groote, University City, and Bernhard Keiser and Charles M. Blair, .lr., Webster Groves, Md, assignors, by mesne assignments, to Petrolite Corporation, Ltd, a corporation or Delaware No Drawing. Application May 9, 1938,

' Serial No. 206,900

7 Claims.

occurring, waters or brines, dispersed in a more or less permanent state throughout the oil which constitutes'the continuous phase of the emulsion. They are obtained from producing wells and from the bottom of oil storage tanks, and

:are commonly referred to as cut oil,"roily oil",

emulsified oil, and bottom settlings.

The object of our invention is to provide a novel and inexpensive process for separating emulsions of the character referred to into their acomponent parts of oil and water or brine.

remain in a quiescent state after treatment, or

is subjected to other. equivalent separatory procedures.

9 The treating agent or demulsifying agent con- 'templated by our process consists of or comprises .an amine of the kind hereinafter described. In-

asmuch as said demulsifying agent consists of a chemical compound or composition of matter, we have herein described with considerable particularity the raw materials entering into the manufacture of said compound and the method employed to produce the same. Said demulsifying agent may be in the form of the amine itself or in the form of the amine base derived by contact with water, or in the form of a' salt. Said amine is. characterized by the fact that it is derived from a blown oil of the kindhereinafter described in such a manner that the blown oil radical or residue (the oxy-acyl radical) is attached to the nitrogen atom of the amine through a carbon atom chain, which carbon atom chain in turn is alkyl, aralkyl, or alicyclic in nature. Said composition and the method of manufacturing the same will be subsequently described in detail. I

It has long been known that various animal, vegetable, and marine oils can be blown or oxidized so'asto yield materials which differ in chemical and physical properties and characteristics from the parent materials from which they were derived. The oxidation process is generally conducted by means of moist or dry air,

ozone, ozonized air, or a mixture of the same.

It may be conducted at atmospheric pressure, or may be conducted under increased pressures of several atmospheres or more. Oxidation may be conducted at relatively low temperatures, for instance, 100 C. or 130 C. or may be conducted at a much higher temperature. Oxidation may be conducted in absence of catalysts, or in presence of catalysts. Such catalysts may consist of metallic salts, such as cobalt or'manganese oleate, or may consist of organic material, such as alpha pinene or the like. Oxidation may be conducted in a relatively short time, such as 20 hours, or may require200 hours or more.

The blown or oxidized oils are generally selected from unsaturated oils of the non-drying type, or the semi-drying type, including the marine oils, such as marine mammal oils, etc. They are rarely selected from the active drying 'oils, such as linseed oil and perilla oil. Although glycerides of saturated acids, such as stearin or palmitin may be oxidized, such blown materials seed oil, peanut oil, corn oil, olive oil, and various marine oils, such as sardine, herring, sperm, menhaden, and pilchard oil.

When an unsaturated fatty acid or oil, for instance, olive oil, is blown or oxidized with air, hydroxyl groups are formed at the ethylene linkage. This is particularly true if oxidation is car-'- ried out with moist air. It is believed that oxygen is first absorbed so as to saturate the ethyl--. ene linkage, and that further reaction takes place with water to produce two hydroxyl groups. Whether or not this is the correct explanation, it isknown that hydroxyl groups are formed.

For instance, Chemistry of the Oil Industry. by Southcombe, 1926, page 181, in speaking of blown (oxidized) oils, states as follows:

' Hy 1 groups are unquestionably formed, as the siderable rise in acetyl value proves.

Patents which describe conventional blown oils or conventional methods of making various blown oils for various purposes (including in some instances, for the purpose of demulsifying. crude oils) include the following:

U. S. Patent No. 1,929,399, dated October 3,

1933, to Fuchs; U. S. Patent No. 1,969,387, dated- August 7, 1934, to Tumbler; U. S. Patent No. 2,023,979, dated December 10, 1935, to Stehr; U. S. Patent No. 2,041,729, ,dated May 26, 1936,

to Seymoun'and U. S. Patent No. 1,984,633, dated.

December 18, 1934, to De Groote and Keiser.

Insofar that the material or composition we prefer to use as the demulsifying agent of our process is derived from blown castor oil, an effort will be made to describe said material or compound in considerable detail. Mild oxidation of castor oil (see Chemical Technology and Analysis of Oils, Fats, and Waxes, by Lewkowitsch, 6th edition, vol. 2, p. 406) produces relatively small modifications in certain importantchemical indices, such as the iodine value, the acetyl value, and the saponification value. drastic oxidation takes place, either by continued 'mild oxidation from the very beginning of the 9 reaction, as induced by either a highertemperature of reaction, or by the presence of a catalyst, such as alpha pinene, manganese ricinoleate, etc., then one obtains an oxidized oil having characteristics which clearly indicate that drastic oxidation has taken place. These indices of drastic oxidation are a relatively low iodine value, suchas' or less, and may be as low as 40. or thereabouts; an acetyl value of approximately 160 to 200; an increased viscosity; a specific gravity of almost 1, oreven a trifle over 1 'at times; and in absence of other coloring matter, a deep orangecolor.

Drastically oxidized castor oil can be prepared by well known methods, or such products can be purchased on the open market under various trade names, such as "blown castor oil, "bodied castor oil, blended caster oil,"blended bodied caster orll", processed castor oil", oxidized cas-' tor oil", "heavy castor oil", viscous castor oil,

'fatty acids. Blown'ricinoleic acidrnay be de-. rived in the manner indicated in U. 8. Patent No. 2,034,941, dated March 24, 1936, to DeGroote,

'Keiser and Wirtel. It should be noted that blown oils in the broad generic senseherein employed yinclude notonly the products derived by oxidadated March 1, 1933, to Hinrichs. Reference is also made to polymerized castor oil or similar oils of the kind disclosed in copending application, Ser. No. 59,090, filed January 13, 1936; by Ivor M. Colbeth. It might also be desirable to point out that the expression blown oil" as herein used,- contemplated blown unsaturated liquid waxes, such as blown sperm oil. It is understood that in the appended claims the expressions blown oil or blown oil fatty acids are used in this broad sense to include all the various materials such as esterified blown fatty acids.

In such instances where blown or polymerized acids are used, it will become apparent that these materials must be converted into an ester before reaction with an amine as subsequently described. For instance, blown castor oil fatty acids, or polymerized ricinoleic acid can be converted into the ethyl ester, methyl ester, propyl ester, cyclohexyl ester, ethylene glycol ester, glyceryl ester, or any suitable ester by means of conventional esteriflcation processes. We desire specifically to point out that the 'estolides of blown oils, as described in U. S. Patent No. 2,079,762, dated May 11,1937, to De Groote and Keiser, are not suitable to be employed in the present process, even after conversion into a completely esterified material by means of a selected alcohol by conventional processes. We have found that when a blown oil is converted into an estolide, such product no longer contains the typical blown oil acidic material. Such estolides are satisfactory demulsifying agents as such. but are not adaptable as raw materials for the manufacture of the amine employed in the present process.

In preparing the demulsifying agentemployed in the present process, we'prefer to produce an amine by reaction with a drastically oxidized castor oil having approximately the following characteristics:

Acid number 13.2 to 25.0 Saponiiication number 230.5 to 274.0 Iodine number 43.5 to 55.0 Acetyl number 164.0 to '192'.0 Hydroxyl value 188.0 to 220.0 Percent unsaponifiable matter 1.1 Percent nitrogen 0.0 Percent S03"-.. 0.0 Percent ash Trace Our usual procedure is to eliminate carboxylic acidity of a blown oil by means of a conventional esterifieation reaction. For instance, in referring to the analysis of the blown castor oil above, it will be seen that such product contains acidity equivalent to 5-10% of the total saponi liable value. esterification with an alcohol, such as methyl alcohol, ethyl alcohol, propyl alcohol, etc. On the other hand, insofar that glycerine is the naturally occurring alcohol present in most oils and fats, and also insofar that glycerine is non-volatile, it-is our preference'to add sufiicient glycerine to'such blown oil and keep it agitated at a tem- 'perature of approximately 125-170 C. until carboxylic acidity disappears.

The blown oils in their various forms, that is, in the ester form, salt form, or acid form, act similarly to fatty acids and their compounds. The typical reactions of fatty acids and amines, par- Such acidity can beremoved byticularly primary or secondary amines, may be indicated by the following:

(A) Salt formation R.COOH+RNHH [HHRNHlOGCR (B) Amide formation R.COOH+HR'NH RCO.NR'H

(C) The third type of reaction involves the fatty acid in the form of a salt so as to produce amino fatty acids. It is to be noted that blown oils can be reacted in such a manner and that the products soobtained are described in U. S.

Patent No. 2,077,230, dated April 13, 1937, to 1 De Groote and Keiser.

(D) It has been suggested that certain blown oils contain aldehydic acids. To the extent that aldehydic acids are present, certain amines, particularly primary or secondary amines, can enter into reactions which are characteristic of the aldehyde radical and would have no connection whatsoever with blown oils which do not contain aldehydic acids. It is to be noted that as far as we are aware, the blown oils which we have employed in the manufacture of the preferred demulsifying agent are free from any aldehydic acids, and even if aldehydic acids are present, an amine of the kind herein contemplated would not be formed by virtue of reaction with the aldehydic group alone. As to reactions of the type involved in the ammonolysis of aldehydic acids, reference is made to U. S. Patent No. 2,079,764, dated May 11, 1937, to De Groote and Keiser.

(E) Still another type of reaction involves fatty acids and a tertiary alkylolamine or its functional equivalent, such as a tertiary hydroxy alicyclic amine. Such reaction may be indicated in the following manner:

derivatives of the fatty acids as they occur in' the blown oil, but rather at the best 'it would result in, derivatives of the estolides. For this reason, materials of the kind employed as demulsifying agents in the present process cannot be obtained from liberated blown oil fatty acids but must be obtained from the blown oils them-.

' selves. This is comparable to the situation indicated in our copending application, Ser.. No. 180,992, filed December 21T193'7, in which it is shown thatcertain amines of a comparable type can be derived from triricinolein, diricinolein,

' monoricinolein, ethyl ricinoleate, and the like,

but cannot be derived from ricinoleic acid because polyricinoleic' acid would be formed.

' form with hydroxy tertiary amines,-one obtains materials of the kind characterized by the fact that the fatty acid radicals derived from the blown oil are present in the amine compound in an esterified form. Such form is substantially unaltered as compared with the original form as presentin the blown oil itself. It may be well to point out two facts in regard to use of the blown oils and the fatty acids derived therefrom. We have previously pointed out that ordinary blown oils show some acidity and that our present reaction is concerned between hydroxy tertiary amines and esters, and not fatty acids. However, since many conventional blown oils contain as little as 5% free acidity, calculated in the usual manner, it is obvious that this small acidity may be ignored and that for practical purposes the preliminary step intended to insure complete esterification may be eliminated.

Secondly, we have referred to the acids present in blown oil as fatty acids)" This is purely a matter of convenience. The expression fatty acids as usually employed is intended to include unsaturated fatty acids of the kind which occur in'natural oils and fats in the formof esters such as the-glycerides. These fatty acids are sometimes referred to as higher fatty acids, and occur in oils such as olive oil, cottonseed oil, soy bean oil, corn oil, castor oil, neat's-foot oil, and in marine oils such as menhaden oil, herring oil, sardine oil, pilchard oil, etc.

In some instances these oils or the corresponding fatty acids, may be heated or oxidized so as to produce lower homologues or higher polymeric forms. For instance, ricinoleic acid can be heated in such a manner as to produce hendecenoic acid. C11H22O2, which is a lower homologue of oleic acid. Such materials are not fatty acids in the usual sense, since they do not occur as such in natural oils and fats,.but they are herein considered as fatty acids, since they represent lower homologues or-isologues, and have the characteristic properties of the common fatty acids. They occur in blown oils, obtained by well-known procedure. For instance, when castor oil is heatedand oxidized so as to produce blown or oxidized oil, one may at least partially break down the molecule having 18 carbon atoms into two molecules having, for example, 7 carbon atoms and 11 carbon atoms. Such acids of lower molecular weight may combine in various manners to produce acids of higher molecular weight than naturally occurring fatty acids. Hence the expression fatty acids is herein employed to refer not only to naturally occurring fatty acids of the kind previously described, but also those kindred products of higher p or lower molecular weight which appear cogenerically in conventional blown oils in the form of free acids or esters. I

As to the production of the amines employed I as demulsifying agents in the present process, attention is directed to our copending application, Ser.. No. 180,993, filed December 21, 1937. In view of the somewhat complicated chemical :ature of the demulsifying agents employed. it may be well to point out the general type of reaction-involved in their manufacture. For convenience, the fatty acids of blown oils will be considered as R..COOH and the blown oil itself will be considered as the glyceride. of these .ma-

. terials and indicated thus:

(R.COO) 3C3H5 Purely as amatter of simplicity, triethanolamine will be selectedas the tertiary hydroxyamine for reaction with-a selected-blown oil. The reactions taking place in varying molecular. pro

portions may be indicated'in the following manner:-

In the third place, it must be recognized that these compounds are derived only from basic ter- 11.000 02min, aooocgm The manufacture of these compounds is relatively simple. The selected blown oil and the selected hydroxy tertiary amine are mixed in suit able proportions and heated at some point above the boiling point of water, for instance, 110 C.,

and at a point below the decomposition point of the amine, or the blown oil, for instance, 180 C.,

for a suitable period of time, such as 2 to'8 hours. Mild agitation is employed. A catalyst such as sodium oleate, sodium carbonate, caustic soda, etc., may be present in amounts of about onehalf of one percent or less. It is to be noted that the blown oils are always in ester form and are not in acid form, thus are not subject to decomposition of the kind which occurs when one attempts to directly react a blown oil fatty acid with a tertiary alkylolamine. to be noted that this reaction does not take place to any appreciable extent if the blown oil has been converted into a soap or salt. It is obvious that the blown oil fatty acids must be in the form ,of an ester, preferably a glycerylester, although some other esterified form, for instance, a derivative of a monohydric'or dihydric alcohol, could be employed.

Four additional facts must be borne in mindin regard to these compounds. In the first place,

these amines which are employed as demulsifying agents in the present process are not quaternary ammonium bases or salts thereof. The expression ,quaternary ammonium is properly and conventionally applied to compounds in which all four hydrogen atoms of the ammonium radical NH; have been replaced by a hydrocarbon radical or oxyhydrocarbon radical as, for' example, in

trimeth'yl phenyl ammonium hydroxide.

Secondly, an important characteristic which must be recognized is that these amine compounds are not amides. It has been previously pointed out that an amide formation involves a product in which there 'isa direct linkage between the carboxylic carbon atom and the nitrogen atom in the amine. Thisis not the case in the compounds employed as demulsifying agents in the present process.

It is furthermore tiary aminea, The word "basic is employed to exclude amines having little or no basicity such as the ordinary aromatic amines or any amine having at least one aryl radical .directly joined to the amino nitrogen atom. For this reason, these amine products which are herein contemplated as demulsifying agents and which necessarily are characterized by freedom from any aryl groups as such, cannot be derived from aryl amines. They are derived solely from alkyl, alicyclic, or aralkyl amines having at least one'hydroxyl group present. It is true that-in the aralkyl amines there is an aryl group present, but

it is not directly attached to the nitrogen atom as in the case of aryl amines but in tact reprealkylamine. For instance, we consider benzylamine as being phenmethyl amine.

Finally, it must be recognized that these materials have notlost any basicity in the forms of I the esterified amine-and that they exhibit all the properties of a basic amine, that is, they comsentsnothing more or less than a substituted bine with water to form a base presumably a substituted ammonium compound, but not a quaternary ammonium compound insofar that there is always one unsubstituted hydrogen atom of the ammonium radical present. They combine with various acids to form'salts. For example, they may be combined with acetic acid, hydrochloric acid,- lactic acid, chloracetic acid, nitric acid, butyric acid, phosphoric acid, oxalic' acid,

or any suitable organic or inorganic acid, to form salts. It is understood that the reference in the specification and appended claims to the amines includes the basic form and the acid saltsv as well as the amines themselves. The characteristic demulsifying properties are contributed. by'the ,amine and it is immaterial whether they may be considered as being in any one of the three following forms:

- in which m is 1, 2, or 3, m is 0, 1, or 2, with the proviso'that m+m'=3, andn denotes any small whole number, preferably less than 10, and in the case of triethanolamine, denotes the number 21' In the above formula and in all subsequent formulas, including such as appear in the appended claims, RG represents the blown oil fatty acid, which as has been previously explained, is in reality a collection or mixture of manufacture of blown oils.

If, instead of employing triethanolamine, ethyl diethanolamine, pr a similar amine were employed, then the resulting products would be indicated by the following type formula:

[ noooommml OH.OnHZn)m' N fl Zn+ m" in which m is 1 or 2 m is 0 or 1, m is 1 with the proviso that m+m+m=3; and n has'the same significance as above.

In event that diethylaminoethanol were eniployed, it is manifest that anothr variation of the above formula would appear. It is also possible to obtain compounds from such materials as acetylated triethanolamine in which the acetyl radical has replaced one hydrogen atom of one of the hydroxy ethyl radicals. Acetic acid in this instance may be considered typical of the lower fatty acidswhich have less than '7 carbon atoms. If such monoacetylated triethanolamine were employed, the reaction product would be indicated by the following type formula:

n 2n)m' (R'co.oc,.m..)...-

in which 122 is 1 or 2, m is 0 or 1, m" is 1 or 2, and n has the same significance as mH-m'+m" must be equal to 3.

In the above formula R'CO 'indicates an acyl Furthermore, where the radical CnH2n+1, which is'a typical alkyl radical, appears, it may be-a .methyl -radical, ethyl radical, propyl radical,

butyl radical, amyl radical, hexyl radical, octyl radical, etc. On the other hand, instead of being a monovalent alkyl radical, it may be monovalent alicyclic radical'such as a cyclohexylradical, or it may be an aralkyl-radical,*such as a" benzyl radical. In the claims appended hereto, it is understood that the expression .alkylol includes the hydroxy hydrocarbon radicals whether derived from alkyl, alicyclic, or aralkyl radicals.

It is furthermore understood in the hereto appended claims that the expression hydroxy alkylincludes hydroxy alicyclic as well as hydroxy aralkyl radicals, provided that in the latter the hydroxyl group is attached to the aliphatic side .chain. Attention is also directed to the fact that the tertiary amines involving the dihydroxy propyl radical C3H5 (OH)2 may substitute for'the hydroxy'alkyl radicals of the kind described. It is also understood that alkyl-oxyalkyl radicals are the equivalent of an ordinary alkyl radical, insofar that they might appear in products such as the trihydroxy ethyl ether of triethanolamine which may be indicated by the following formula:

N (C2H4OC2H4OH): See other examples described in U. S. Patent No.

' 1,923,178, dated August 22, 1933 to Ulrich et a1.

Such material would be the obvious functional equivalent of triethanolamine in reactions of the kind contemplated in the manufacture of the demulsifying agents contemplated by our process.

The amine employed as a demulsifying agent in the'present process might be indicated by the following formula:

in which m is 1, 2, or 3, m is 0, 1 or 2, with the proviso that m+m'=3, Tis an alkyl radical or a radical of the type (RCOOalkyl) or a hydroxyl alkyl radical, and R'ICOO represents an acid radical having less than 7 carbon atoms. The expression alkyl is used in the broad sense previously specified, and it is also to be repeated that the amine may be in the form of the base or in the form of a salt.

Suitable bases which may be reacted with blown oils or completely esterified blown oils or esterified blown fatty acids to produce the demulsifying agent employed in the present process include; triethanolamine, 'diethanolalkylamines, such as diethanol 'ethylamine, diethanol propylamine,

-etc.; tertiary glyceryl amines, such as monoglyceryl diethylamine, monoglyceryl dipropylamine, diglyceryl propylamine, triglycerylamine,

etc. Other examples include diethanol methylamine, tripropanolamine, dipropanol methylamine, cyclohexanol diethanolamine, dicyclohexanol ethanolamine, cyclohexyl diethanolamine, dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyl diethanolamine, dibenzyl ethanolamine, benzyl dipropanolamine, tripentanolamine, -trihexanolamine, ethyl hexyl ethanolamine,- octadecyl diethanolamine, polyethanolamine, etc.

v In indicating the various hydroxylated tertiary amines of the non-aryl type which may be employed to produce the amine contemplated as then it is understood that such materials. would not represent a hydroxy tertiary amine within the meaning or scope as herein employed. If, on the other hand, triethanolamine were treated with lactic acid so as to give monolactyl triethanolamine of the following composition:

CH|CH.C-O-'CH4 then such compound would be included due to the presence of one or more hydroxyl radicals attached to the alkyl radicals.

Example I Blown castor oil of the kind previously de scribed in detail is employed. For sake of con venience, its molecular weight is considered as being 1000. Commercial triethanolamine and blown castor oil in the proportion of one mole of blown castor oil to three moles of triethanolamine are heated to a temperature between 150 and 180 C. for about 2 hours. Mild agitation is employed. The reaction product so produced may be used'as suchor may be converted into the acetate by the addition of the maximum amount of glacial acetic acid which can be added so without causing acidity to methyl orange indicator. Generally speaking,.this will require about three moles of glacial acetic acid, .or slightly less.-

Example II Triglycerylamine (tri-dihydroxy propylamine) is substituted for triethanolamine in Example I.

Example III Diamyl monoglycerolamine (l-di-amyl amino propane 2, 3, diol) is substituted for triethanolamine in Example I.

Example IV Dicyclohexylamine is reacted with glycerol monochlorhydrin to give monoglyceryl dicyclo-' 'hexylamine. This product is substituted for triethanolamine in Example I.

Example V Dibenzylamine is reacted with glycerol monochlorhydrin-- to produce monoglyceryl dibenzylamine. This product is substituted for triethanolamine in Example I.

Blown rapeseed "oil of commerce, molecular weight figured as 990, is substituted for blown castor oil employed in Examples I-VI inclusive.

Example VIII 7o- Blown cottonseed oil, molecular weight figured as 980, is substituted for blown castor oil in Examples I-VI inclusive.

We desire to emphasize that the products obtained in the above examples may be used in the 75 forr g oe tateg an ine by'direct contact with an cresol,.anthracene oil, etc. Alcohols, particularly aliphatimalcohols, such as'methyl; alcohol, ethyl emulsion without contact with water. They may be contacted with water,'th at is, used in the form of a solution so as to produce in a greater or lesser degree the amine base., Furthermore, any of the products above described may be combined 5 with a suitable acid. Acetic acid may be em-v ployed. Hydrochloric acidis particularly desirable. -In some instances, acids such as oleic. acid may be employed to give a suitable salt.

In examining the method of manufacture of 1 these compounds aspreviously illustrated, it is apparent that certain by-products appear such as glycerine, monoor diglycerides, etc. Froma practical standpoint it is unnecessary to separate these cogeneric materials, though it would-be pos- 15 sible to do so by conventional processes. It is ,quite possible that these materials which appear as a part of the reaction mass'contribute to a greater or lesser degree to the demulsifying power of the amine body. It may be that some of these 50 materials which appear in the reaction mass can-. not be completely identified as to their form. For instance, it is at once possible to see that condensation products might be formed under proper conditions between amines of the kind as contemplated as demulsifying agents in the present process and either glycerol or triethanolamine, by virtue of an ether linkage. In view of this fact, in the appended claims the demulsifying agent will not only be described in terms of the chemi- 3o cal structure of the amine, but also in terms of the method of manufacture. The purpose of the claims which are characterized by reference to the method of manufacture is to specifically include .the general reaction mass produced in the manu- 35 facture of the amine-bodies.

One should not lose sight of the fact, however, that the present invention isconcerned particularly with the employment of certain chemical compounds of definitely stated composition which a are' present in significant or predominant amounts in'themixtures obtained by the reactions described.- Needless to say, the employment of the selected demulsifying agents in the art of breaking crude oil emulsions is not limited to any particular method of manufacture except in the appended claims, in which specific reference is made to manufacturing procedure.

Attention is directed to the fact that the word amidiflcation" has been applied to the reaction involving the replacement of an amino hydrogen atom by an acyl radical without conventional limitation to areaction'involvi'ng ammonia. The

replacement of the amino hydrogen atom of a gasoline, kerosene, stove oil, a coal tar product,

such as benzene, toluene, xylene, tar acid oil,

alcohol, denatured alcohol, propyl"; alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the'refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble-f-orm, or in a form exhibiting both oil and water solubility. may be used in a form which exhibits relatively limited water solubility and relatively limited oil solubility. However, since such reagents are sometimes used in a ratio of l to 10,000 or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of our process.

We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our process is based upon itsability to treat certain emulsions morcadvantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practicing our process, a treating agent or demulsifying agent of thekind above described is brought into contact with or caused to act upon'the emulsion to be treated, in any of the various ways or by any of the various apparatus now generally used to resolve or break petroleum by reaction, under substantially anhydrous conditions, between a blown oil and a non-aryl tertiary hydroxy amine withinthe molal ratio of 1:1 and 1:3, at a temperature above the boiling point of water and'below the point of decomposition; said reaction being conducted in a manner to yield a substantial quantity of basicmaterial in which the blown oil fatty acid radical is attached tothe basic nitrogen atom through a carbon atom chain; with the added proviso that in said basic material the ratio of said acid radical Sometimes they;

by reaction, under substantially anhydrous conditions, between a blown oil and triethanolamine Within the molal ratio of 1 1 and 1 :3, at a temperature above the boiling point of water and below the point of decomposition; said reaction being conducted in a manner to yield a substantial quantity of basic material in which the blown oil fatty acid radical is attached to the basic nitrogen atom through a carbon atom chain; with the added proviso that in said basic material the ratio of said acid radical to the amino nitrogen atom shall be at least 1:1 and not more than 3:1; and said basic material being further characterized by absence of amide and polyamino radicals.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a composition of matter derived by reaction, under substantially anhydrous conditions, between a blown castor oil and triethanolamine within the molal ratio of 1:1 and 1:3, at a temperature above the boiling point of- Water and below the point of decomposition; said reaction being conducted in a manner to yield a substantial quantity of basic material in which the blown oil fatty acid radical is attached to the basic nitrogen atom through a carbon atom chain;v with the added proviso that in said basic material the ratio of said acid radical to the amino nitrogen atom shall be at least 1:1 and not more than 3:1; and said basic material being further characterized by absence of amide and polyamino radicals.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a chemical compound of the type indicated by the formula:

in which m is 1, 2, or a, m is 0, 1, or 2, with the proviso that m+m'=3, T is selected from the class consisting of alkyl radicals, radicals of the type (RlCOOalkyl) and hydroxyl alkyl radicals, and R.COO represents the blown oil fatty acid radical,'and R'.COO'is an acid radical having less than '7 carbon atoms. 7

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a chemical compound of the type indicated by the formula:

.in which mis 1 or 2, and m is 1 or 2, with the proviso that m+m=3, 'I is a hydroxy alkyl radical, and R.COO is a blown oil fatty acid radical.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifying agent comprising a chemical compound of the type indicated by the formula:

in which m is 1, or and m is 1, or 2, with the proviso that m+m'=3, T is a hydroxy ethyl radical, and R.COO is a blown oil fatty. acid\ radical 7. A process for breaking petroleum emulsions of the'water-in-oil type, characterized by subjecting the emulsion to the action of a demulsify proviso that m+m'=3, T is a. hydroxy ethyl my agent comprising a chemical compound of radical, and R'.COO is a, blown oilfatty acid the type indicated by the formula; radical derivedtrom castor oil.

' [,(R'.0oo.o,m N MELVIN DE GROOTE. 5 (TL-u] BERNHARD KEISER.

in which m is 1 or 2, and m is 1 or 2, with the CHARLES BLAIR, 

